Sorbent devices

ABSTRACT

Sorbent material sheets provide for enhanced performance in vapor adsorbing applications over conventional canisters and other emissions control equipment. The sorbent material sheets can be formed as part of a small, lightweight canister, or can be integrated into a fuel tank. The sorbent material sheets can also be used as part of an onboard refueling vapor recovery system to control volatile organic compound emissions from fuel tanks of gasoline vehicles, such as automobiles.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. Non-Provisionalpatent application Ser. No. 15/885,317 filed on Jan. 31, 2018, whichclaims priority to U.S. Provisional Application No. 62/452,704 filed onJan. 31, 2017, the entirety of which are incorporated by referenceherein.

GOVERNMENT INTERESTS

Not applicable

Parties to a Joint Research Agreement

Not applicable

INCORPORATION BY REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC

Not applicable

BACKGROUND

Evaporative emissions from gasoline and other liquid hydrocarbon fuelsare a significant source of air pollution because the varioushydrocarbons contained in the fuels can form photochemical smog onexposure to sunlight. The compounds of this smog and the hydrocarbonsthemselves cause degrading health effects in humans and animals as wellas environmental damage. Evaporative emissions are especiallyproblematic during vehicle refueling because the “empty” fuel tank isactually filled with fuel vapors, and the act of filling the tank withliquid fuel displaces the vapors from the tank. Evaporative emissionsalso occur when the fuel within the tank is heated, such as from hotambient conditions or from nearby hot exhaust system components. Withoutcontrols, fuel vapors would be released as pollution into theatmosphere.

In the automotive sector, gasoline vapors are typically recovered duringrefueling by an Onboard Refueling Vapor Recovery system (ORVR). Thesedevices include multiple components which are designed to capture thedisplaced vapors from gasoline refueling and allow the engine to burnthem at a later time. Vapors remain sealed within the fuel tank byspecially designed tanks and fuel filler neck, and excess vapor iscaptured and adsorbed within a chemical canister. During engineoperation, the Engine Control Unit (ECU) permits adsorbed vapors to bereleased from the canister and into the engine fuel system, burning thegasoline vapors as normal and permitting the canister to be used again.

While ORVR systems have been successful in reducing vapor emissions,they still have drawbacks. The chemical canisters are filled with looseadsorbent particulates such as activated carbon or charcoal, which canbe messy to handle and package. These canisters are bulky and heavybecause the adsorbent particulates cannot physically support themselves,and because stringent emissions regulations now prohibit the release ofeven small amounts of vapor emissions, which requires higher adsorbentcapacity. Manufacturing, maintenance and disposal of the canisters isalso cumbersome because of the loose adsorbent particulates, and thecomplexity of ORVR devices increases the cost of each vehicle whilecutting into valuable passenger and cargo space. With automakersdemanding lighter weights from all components to meet increasing fuelefficiency targets, as well as cost reductions and greater passenger andcargo space, there is a need for new ORVR devices and that are smaller,lighter, simpler, and more cost effective, while still complying withstricter emissions targets.

SUMMARY OF THE INVENTION

In one embodiment, the invention discloses sorbent material sheets thathave improved performance over the equivalent amount of adsorbentcompound provided as a powder.

In another embodiment, the invention discloses sorbent material sheetsenclosed within a housing.

In another embodiment, the invention discloses sorbent material sheetsthat omit the housing and which are instead contained directly within afuel tank.

In another embodiment, the invention discloses an emissions controlsystem, such as an ORVR which includes sorbent material sheets. Thesorbent material sheets within the ORVR may be enclosed within a housingor the housing may be omitted.

The invention is also directed to the embodiments listed below:

1. A sorbent material sheet product, comprising

-   -   at least two sorbent material sheets, each of which has a        defined upper surface and lower surface which have a combined        total surface area, and    -   wherein each sorbent material sheet comprises a sorbent material        and a binder, and    -   wherein each sorbent material sheet is stacked and arranged such        that adjacent upper and lower surfaces of the separate sheets        are substantially parallel and are aligned to allow fluid flow        at least between the adjacent upper and lower surfaces.

2. The sorbent material sheet product of embodiment 1, wherein thesorbent material sheet product has a BWC stacking multiplier ratio ofabout 1.1 to about 1.3, wherein the BWC stacking multiplier ratio isdefined by the formula:BWC stacking multiplier ratio=[(measured BWC of entire sorbent materialsheet product)/(measured BWC of individual sorbent material sheetoutside of product)]/number of sorbent material sheets in the sorbentmaterial sheet product.

3. The sorbent material sheet product of embodiment 1, wherein theindividual sorbent material sheets, measured individually, have BWCvalues that are 5-15% higher than the BWC of the same weight of sorbentmaterial in pelletized or powdered forms.

4. The sorbent material sheet product of embodiment 1, wherein at leastone of the sorbent material sheets are configured as being flat, woundin a spiral cylinder, wound in an elliptical form, wound in an elongaterectangular bar, folded, laminated in an “S” shape, formed as concentriccylinders, formed as concentric ellipses, formed as a concentricrectangular bar, or as combinations of these forms.

5. The sorbent material sheet product of embodiment 1, wherein at leastone of the sorbent material sheets has raised and/or depressed portions.

6. The sorbent material sheet product of embodiment 5, wherein theraised and/or depressed portions are present on adjacent sheets and arenested.

7. The sorbent material sheet product of embodiment 5, wherein theraised and/or depressed portions are present on adjacent sheets and arenot nested.

8. The sorbent material sheet product of embodiment 1, wherein thesorbent material sheet product has a void volume of about 10% or less.

9. The sorbent material sheet product of embodiment 1, wherein eachindividual sorbent material sheet has a density of about 0.08 g/cc toabout 1.5 g/cc.

10. The sorbent material sheet product of embodiment 1, wherein thesorbent material sheet product has a BWC greater than about 10 g/100 cc.

11. The sorbent material product of embodiment 1, wherein the sorbentmaterial sheet product has a BWC of about 7.0 g/100 cc to about 30 g/100cc.

12. The sorbent material sheet product of embodiment 1, wherein thesorbent material sheets comprise sorbent material particles having atleast two populations having different average particle diameters, andwherein the average particle diameters of the two populations haveratios of about 1:2 to about 1:10.

13. The sorbent material sheet product of embodiment 1, wherein theamount of binder and the amount of sorbent material sheet products arepresent in a gradient such that the amount of binder is highest at anouter portion of the sorbent material sheet product, and that the amountof binder is lowest at an inner portion of the sorbent material sheetproduct.

14. The sorbent material sheet product of embodiment 1, wherein at leastone sorbent material sheet include holes, cuts, or apertures.

15. The sorbent material sheet product of embodiment 1, wherein thebinder comprises polytetrafluoroethylenes (PTFE or TEFLON),polyvinylidene fluorides (PVF₂ or PVDF), ethylene-propylene-diene (EPDM)rubbers, polyethylene oxides (PEO), UV curable acrylates, UV curablemethacrylates, heat curable divinyl ethers, polybutylene terephthalate,acetal or polyoxymethylene resin, fluoroelastomers, perfluoroelastomers(FFKM) and/or tetrafluoro ethylene/propylene rubbers (FEPM), aramidpolymers, para-aramid polymers, meta-aramid polymers, poly trimethyleneterephthalate, ethylene acrylic elastomers, polyimide, polyamide-imides,polyurethanes, low density and high density polyethylene, polypropylene,biaxially oriented polypropylene (BoPP), polyethylene terephthalate(PET), biaxially oriented polyethylene terephthalate (BoPET),polychloroprene, and copolymers and combinations thereof.

16. A rolled sorbent material sheet product, comprising:

-   -   a sorbent material sheet defining an upper surface and a lower        surface and having a total surface area, and which comprises a        sorbent material and a binder,    -   wherein the sorbent material sheet is spiral wound to form        adjacent sheet layers which allow fluid flow around and between        adjacent sheet layers.

17. The rolled sorbent material sheet product of embodiment 16, whereinthe sorbent material sheet in its rolled form has a BWC that is at least10% higher than the BWC of the same sorbent material sheet in anunrolled form.

18. The rolled sorbent material sheet product of embodiment 16, whereinthe rolled sorbent material sheet product has a BWC that is at least 10%higher than the BWC of a pelletized or powdered form of thesubstantially the same amount of sorbent material in the sorbent sheet.

19. The rolled sorbent material sheet product of embodiment 16, whereinthe rolled sorbent material sheet product has a generally cylindricalshape having a length that is greater than its diameter.

20. The rolled sorbent material sheet product of embodiment 16, whereinthe rolled sorbent material sheet product is wound to an average rolldensity of 500-700 kg/m³.

21. The rolled sorbent material sheet product of embodiment 16, whereinthe rolled sorbent material sheet product has a butane working capacitygreater than about 10 g/100 cc.

22. The rolled sorbent material sheet product of embodiment 16, whereinthe rolled sorbent material sheet product has a butane working capacityof about 7.0 g/100 cc to about 30 g/100 cc.

23. The rolled sorbent material sheet product of embodiment 16, whereinthe rolled sorbent material sheet comprises at least two populations ofsorbent material particles, wherein each of the at least two populationshave different average particle diameters.

24. The rolled sorbent material sheet product of embodiment 16, whereinthe rolled sorbent material sheets comprise sorbent material particleshaving at least two populations having different average particlediameters, and wherein the average particle diameters of the twopopulations have ratios of about 1:2 to about 1:10.

25. The rolled sorbent material sheet product of embodiment 16, whereinthe binder comprises polytetrafluoroethylenes (PTFE or TEFLON),polyvinylidene fluorides (PVF₂ or PVDF), ethylene-propylene-diene (EPDM)rubbers, polyethylene oxides (PEO), UV curable acrylates, UV curablemethacrylates, heat curable divinyl ethers, polybutylene terephthalate,acetal or polyoxymethylene resin, fluoroelastomers, perfluoroelastomers(FFKM) and/or tetrafluoro ethylene/propylene rubbers (FEPM), aramidpolymers, para-aramid polymers, meta-aramid polymers, poly trimethyleneterephthalate, ethylene acrylic elastomers, polyimide, polyamide-imides,polyurethanes, low density and high density polyethylene, polypropylene,biaxially oriented polypropylene (BoPP), polyethylene terephthalate(PET), biaxially oriented polyethylene terephthalate (BoPET),polychloroprene, and copolymers and combinations thereof.

26. A vapor adsorbing canister, comprising:

-   -   The sorbent material sheet product of embodiment 1, and a        housing at least partially encapsulating the sorbent material        sheet product of embodiment 1

27. The vapor adsorbing canister of embodiment 26, wherein the housingis flexible.

28. The vapor adsorbing canister of embodiment 26, wherein the housingcomprises polytetrafluoroethylenes (PTFE or TEFLON), polyvinylidenefluorides (PVF₂ or PVDF), ethylene-propylene-diene (EPDM) rubbers,polyethylene oxides (PEO), UV curable acrylates, UV curablemethacrylates, heat curable divinyl ethers, polybutylene terephthalate,acetal or polyoxymethylene resin, fluoroelastomers perfluoroelastomers(FFKM) and/or tetrafluoro ethylene/propylene rubbers (FEPM), aramidpolymers, para-aramid, meta-aramid polymers, poly trimethyleneterephthalate, ethylene acrylic elastomers, polyimide, polyamide-imides,polyurethanes, low density and high density polyethylene, polypropylene,biaxially oriented polypropylene (BoPP), polyethylene terephthalate(PET), biaxially oriented polyethylene terephthalate (BoPET),polychloroprene, and copolymers and combinations thereof.

29. The vapor adsorbing canister of embodiment 26, wherein the shape ofthe housing substantially conforms to the shape of the enclosed sorbentmaterial sheet product of embodiment 1.

30. The vapor adsorbing canister of embodiment 26, further comprising atleast one structure selected from tubes, inlet ports, outlet ports,sensors, valves, and fluid channels.

31. A vapor adsorbing canister, comprising,

-   -   a. the rolled sorbent material sheet product of embodiment 16,        and    -   b. a housing at least partially encapsulating the rolled sorbent        material sheet product of embodiment 16.

32. The vapor absorbing canister of embodiment 31, wherein the housingis flexible.

33. The vapor adsorbing canister of embodiment 31, wherein the housingcomprises polytetrafluoroethylenes (PTFE or TEFLON), polyvinylidenefluorides (PVF₂ or PVDF), ethylene-propylene-diene (EPDM) rubbers,polyethylene oxides (PEO), UV curable acrylates, UV curablemethacrylates, heat curable divinyl ethers, polybutylene terephthalate,acetal or polyoxymethylene resin, fluoroelastomers perfluoroelastomers(FFKM) and/or tetrafluoro ethylene/propylene rubbers (FEPM), aramidpolymers, para-aramid, meta-aramid polymers, poly trimethyleneterephthalate, ethylene acrylic elastomers, polyimide, polyamide-imides,polyurethanes, low density and high density polyethylene, polypropylene,biaxially oriented polypropylene (BoPP), polyethylene terephthalate(PET), biaxially oriented polyethylene terephthalate (BoPET),polychloroprene, and copolymers and combinations thereof.

34. The vapor absorbing canister of embodiment 31, wherein the shape ofthe housing substantially conforms to the shape of the enclosed rolledsorbent material sheet product of embodiment 16.

35. The vapor adsorbing canister of embodiment 31, further comprising atleast one structure selected from tubes, inlet ports, outlet ports,sensors, valves, and fluid channels.

36. A tank with integral vapor adsorption, comprising:

-   -   a tank structure, and    -   at least one sorbent material sheet which has a defined upper        surface and lower surface which have a combined total surface        area, and    -   wherein each sorbent material sheet comprises a sorbent material        and a binder, and    -   at least one fastening device which fastens the sorbent material        sheet to a surface of the tank that is not regularly immersed in        the volatile liquids contained within the tank.

37. The tank with integral vapor adsorption of embodiment 36, whereinthe fastening device is an adhesive layer which is formed between onesurface of the sorbent material sheet and a wall of the tank.

38. The tank with integral vapor adsorption of embodiment 36, whereinthe adhesive comprises at least one of pressure sensitive adhesives, UVcuring adhesives, thermally curing adhesives, hot melt adhesives,reactive multi-part adhesives, acrylic and (meth)acrylic adhesives,acrylate and (meth)acrylate adhesives, epoxy adhesives in one- ortwo-part formulations, urethane adhesives, and copolymers andcombinations thereof.

39. The tank with integral vapor adsorption of embodiment 36, whereinthe tank further includes at least one fuel pump(s), fuel sendingline(s), fuel return line(s), atmospheric vent line, port(s), valve(s),sensor(s), air inlet(s), open cell foam, baffle(s), bladder(s) andcombinations of those.

40. The tank with integral vapor adsorption of embodiment 36, whereinthe tank is a fuel tank with a “ship in a bottle” configuration.

41. An onboard refueling vapor recovery apparatus comprising the sorbentmaterial sheet product of embodiment 1.

42. An onboard refueling vapor recovery apparatus comprising the rolledsorbent material sheet product of embodiment 16.

43. An onboard refueling vapor recovery apparatus comprising the vaporadsorbing canister of embodiment 26

44. An onboard refueling vapor recovery apparatus comprising the vaporadsorbing canister of embodiment 31.

45. An onboard refueling vapor recovery apparatus comprising the tankwith integral vapor adsorption of embodiment 36.

DESCRIPTION OF DRAWINGS

Not Applicable.

DETAILED DESCRIPTION

Before the present compositions and methods are described, it is to beunderstood that this invention is not limited to the particularprocesses, compositions, or methodologies described, as these may vary.It is also to be understood that the terminology used in the descriptionis for the purpose of describing the particular versions or embodimentsonly, and is not intended to limit the scope of the present invention,which will be limited only by the appended claims. Unless definedotherwise, all technical and scientific terms used herein have the samemeaning as commonly understood by one of ordinary skill in the art.Although any methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of embodimentsof the present invention, the preferred methods, devices, and materialsare now described. All publications mentioned herein are incorporated byreference in their entirety. Nothing herein is to be construed as anadmission that the invention is not entitled to antedate such disclosureby virtue of prior invention.

It must also be noted that as used herein and in the appended claims,the singular forms “a,” “an,” and “the” include plural reference unlessthe context clearly dictates otherwise. Thus, for example, reference to“a combustion chamber” is a reference to “one or more combustionchambers” and equivalents thereof known to those skilled in the art, andso forth.

As used herein, the term “about” means plus or minus 10% of thenumerical value of the number with which it is being used. Therefore,about 50% means in the range of 45%-55%.

As used herein, the term “sorbent material” is meant to encompass allknown materials from any source that are capable of adsorbing liquidsand/or gases. For example, sorbent materials include, but are notlimited to, activated carbon, natural and synthetic zeolite, silica,silica gel, alumina, zirconia, and diatomaceous earths.

As used herein, the term “may” means that the subsequently listedelement may or may not be included in an embodiment. For example, anembodiment that may include a polymer substrate means that theembodiment can include that polymer substrate, but that it is alsocontemplated that the embodiment can exclude the polymer substrate.

As used herein, descriptions and claims of multiple sorbent materialsheets mean that there are multiple, separated sheets, with sides and/orsurfaces in proximity to each other. Alternatively, descriptions andclaims of multiple sorbent material sheets mean that there is only asingle sheet, but that it has been wound or folded over on itself toyield a stacked, wound, or otherwise constructed mass of sheets withsides and/or surfaces in proximity to each other. The term alsoenvisions that multiple sheets are stacked together and then wound orotherwise folded over, forming alternating layers in a single mass.

Embodiments of the invention are directed to devices containing one ormore sheets of sorbent material, sorbent material sheets, and methodsfor making sorbent material sheets and devices containing these sheets.In various embodiments, the sorbent material sheets may be composed of asorbent material and a binder and have a thickness of less than about 1mm. The devices of various embodiments may include a housing and one ormore of sorbent material sheets.

In some embodiments, the devices may have a void fraction of about 10%or more of the total volume of the housing.

The Sorbent Material Sheets

The sorbent material sheets of the invention may include any of thesorbent materials described above including, but are not limited to,activated carbon, natural and synthetic zeolite, silica, silica gel,alumina, zirconia, and diatomaceous earths, and in certain embodiments,the sorbent material sheets may be composed of activated carbon. Thesorbents may be used alone or in combination.

The activated carbon may be of various grades and types selected basedon performance requirements, cost, and other considerations. Theactivated carbon may be granular from reagglomerating a powder, granularfrom crushing or sizing nutshells, wood, coal or pellets created byextrusion, or activated carbon in powdered form. The activated carbonmay be formed by processes of carbonization and activated. The rawmaterial, such as wood, nutshell, coal, pitch, etc. is oxidized anddevolatized, with steam and/or carbon dioxide gasified to form the porestructure in the activated carbon which is useful for adsorption. Theinitial oxidation and devolatilization process may include a chemicaltreatment with a dehydrating chemical, such as phosphoric acid, sulfuricacid, sodium hydroxide, potassium hydroxide, and combinations of those.

A variety of activation processes are known in the art. The most usefulprocesses for providing activated carbon for the sorbent material sheetsof the claimed invention involve a step of providing wood and/or woodbyproduct, acid treating the wood and/or wood byproducts by exposure tophosphoric acid, and carbonizing the wood and/or wood byproducts usingsteam and/or carbon dioxide gasification. This process results inactivated carbon particles having the highest butane working capacity(“BWC”), which is a measure of activated carbon performance. Moredetails of the BWC testing and results are described in the Examples.

The activated carbon may be formed from materials including bagasse,bamboo, coconut husks, peat, wood such as hardwood and softwood sourcesin the form of sawdust and scrap, lignite, coal and coal tar, petroleumpitch, asphalt and bitumen, corn stalks and husks, wheat straw, spentgrains, rice hulls and husks, nutshells, and combinations thereof.

The sorbent material sheets may further include one or more binders.Embodiments are not limited to particular binders, which can includepolytetrafluoroethylenes (PTFE or TEFLON), polyvinylidene fluorides(PVF₂ or PVDF), ethylene-propylene-diene (EPDM) rubbers, polyethyleneoxides (PEO), UV curable acrylates, UV curable methacrylates, heatcurable divinyl ethers, polybutylene terephthalate, acetal orpolyoxymethylene resin, fluoroelastomers such as perfluoroelastomers(FFKM) and tetrafluoro ethylene/propylene rubbers (FEPM), aramidpolymers such as para-aramid and meta-aramid polymers, poly trimethyleneterephthalate, ethylene acrylic elastomers, polyimide, polyamide-imides,polyurethanes, low density and high density polyethylene, polypropylene,biaxially oriented polypropylene (BoPP), polyethylene terephthalate(PET), biaxially oriented polyethylene terephthalate (BoPET),polychloroprene, and copolymers and combinations thereof. The binderscan be thermoplastic or thermosetting as conditions require, and caninclude mixtures of thermoplastic and thermosetting compounds.

The amount of binder may be about 2% to about 30% by weight of the totalcomposition, and in certain embodiments, the amount of binder may beabout 2% to about 20% by weight or about 2% to about 10% by weight ofthe total composition, or any individual amount or range encompassingthese example amounts. In some embodiments, the sorbent material sheetsmay include a solvent, which may generally be present in small,residual, amounts of, for example, less than 10%, less than 5%, or lessthan 2% and greater than about 0.1% or 0.2% by weight. In particular, insome embodiments the sorbent material sheets may have no (0%) solvent.

In some embodiments, the sorbent material sheets may have a thickness ofless than about 1 mm, about 0.01 mm to about 1.0 mm, about 0.02 mm toabout 0.90 mm, about 0.05 to about 0.95 mm, about 0.05 to about 0.90 mmor any individual thickness or range encompassed by these exampleranges. The sorbent material sheets of various embodiments may have adensity of about 0.05 g/cc to about 2.0 g/cc as measured by the particledensity test, and in other embodiments, the sorbent material sheets mayhave a density of 0.08 g/cc to about 1.5 g/cc, about 0.1 g/cc to about1.3 g/cc as measured by the particle density test, or any density orrange encompassed by these example ranges. In some embodiments, thesorbent material sheet may have a resistivity of less than 20 ohm-cm,and in certain embodiments, the sorbent material sheets may have aresistivity of about 10 ohm-cm to about 20 ohm-cm, about 8 ohm-cm toabout 18 ohm-cm or any individual resistivity or range encompassed bythese example ranges. The BWC for each sorbent material sheet may begreater than about 10 g/100 cc, and in some embodiments, the BWC may befrom about 7.0 g/100 cc to about 30 g/100 cc, about 8.0 g/100 cc toabout 25 g/100 cc, about 10 g/100 cc to about 20 g/100 cc, about 10g/100 cc to about 15 g/100 cc, about 11 g/100 cc to about 15 g/100 cc,about 12 g/100 cc to about 15 g/100 cc or any individual BWC or rangeencompassed by these example ranges. In other examples, the BWC may beabout 9 g/100 cc to about 15 g/100 cc, about 12 g/100 cc to about 20g/100 cc, about 13 g/100 cc to about 20 g/100 cc, about 14 g/100 cc toabout 20 g/100 cc, or about 15 g/100 cc to about 20 g/100 cc. It is alsocontemplated that any of the endpoints of the above ranges may becombined to form new and distinct ranges.

The sorbent material sheets of the present invention have higherperformance as measured by the BWC than conventional sorbent materialswhich are provided in powders or other particulate forms.

The sorbent material sheets of embodiments can be made by any process.In some embodiments, sorbent material sheets can be made by pulverizinggranular or pelletized sorbent material to a powder, mixing the powderwith a binder to form a mixture, heating and blending the mixture, androlling the mixture to form the sorbent material sheet. The step ofpulverizing may produce sorbent particles having an average particlediameter of about 0.001 mm to about 0.2 mm, about 0.005 mm to about 0.1mm, about 0.01 mm to about 0.075 mm, or any individual particle diameteror range encompassed by these example ranges, and in certainembodiments, the pulverized sorbent particles may have an averageparticle diameter of about 0.001 mm to about 0.01 mm. The step of mixingthe powder with a binder may include mixing the sorbent particle powderwith about 2% to about 20% by weight or about 2% to about 10% by weightof the total composition, or any individual amount or range encompassedby these example ranges. Heating can be carried out at any temperaturesufficient to remove residual solvent such as, for example, about 50° C.to about 200° C.

The sorbent material sheet of the invention may include variousdistributions of different sized particles to increase the packingefficiency of the powder within the sorbent material sheets. Theselection of different sized particles can also improve rheologicalproperties of the powder and surrounding binders, which allows improvedmixing and uniform particle distribution before formation of the sorbentmaterial sheets. In some embodiments, the particles of the sorbentmaterial sheet may have a single particle size distribution, and inother embodiments, the particles may have two different particle sizedistributions. In further embodiments, the particle may have at leastthree different particle size distributions.

The mean particle sizes of the at least two different particlepopulations, each having a particular size distribution, may be selectedso that they have a ratios of between about 1:1 and about 1:15: In otherembodiments, the mean particle sizes of the two different particlepopulations may have a ratio of about 1:2 to about 1:10. The meanparticle sizes may also have a ratio of about 1:2 to about 1:5, orcombinations of any of the above listed ratios.

The sorbent material sheets have significantly higher sorbent capacitythan prior art fuel vapor recovery canisters for a given volume andweight. This capability can be utilized in various ways. In someembodiments, the sorbent material sheets can provide enhanced pollutioncontrols in jurisdictions where such high levels of control arerequired. In other embodiments, the overall size, cost, and weight ofthe ORVR can be reduced for a specific level of performance. In furtherembodiments, an ORVR adsorption device can be designed which hasincreased performance over conventional adsorption canisters, therebyallowing the designer to omit costly and complex returnless fuel pumpsystems which would otherwise be required to reduce evaporativeemissions. Higher performance adsorption devices may also render activecondensing vapor systems unnecessary, which avoids the size, weight, andcost of compressor pumps and condensate storage tanks. It should beunderstood, however, that the ORVR adsorption device using the sorbentmaterial sheets of the invention can also be combined with these devicesfor exceptionally high performance and a minimal size, weight, and costpenalty over conventional systems.

The sorbent material sheets may be configured together in a variety ofways depending on the physical space that they must conform to, therequired device performance, and the features which are included inproximity to the sheets. In some embodiments, the sheets may becorrugated, include folds, and/or include holes or apertures to increasethe surface area of the sorbent material sheets that is exposed to thepassing fluid, therefore increasing performance for a given total sheetsurface area. The various corrugations, folds, holes, and apertures canalso be sized and placed to make way for internal and external features,such as fluid channels, tubing, sensors, and valves. The folds of thesorbent material sheets may take a variety of forms, such as a spiralwrapped configuration in either a cylindrical or elliptical form. Thefolds may also be in the form of an “S” shape, or a convex or concave“C” shape depending on the required device dimensions and/or any otherrequired internal or external features. The sorbent material sheets mayalso be stacked in a flat or curved configuration, and the stackedsheets may be square, rectangular, circular, oval, or other irregularshape as needed to fit the space intended. This, in combination with thehousing features discussed below, enables devices formed from thesorbent material sheets to fit in smaller, more irregularly shapedspaces than prior art canister devices, which maximizes vehicle interiorspace.

In addition to the above described configurations, the sorbent materialsheets may also have surface features. In some embodiments, the sorbentmaterial sheets may include raised portions, and in other embodiments,the sorbent material sheets may include depressed portions. Thesesurface features may be combined within the same sheet. The inclusion ofraised and/or depressed portions in the sheets may be utilized to formvarious configurations between the sheets as they are stacked, wrapped,and so forth. For instance, the sheets can be aligned so that the raisedand/or depressed portions nest with each other, which brings theadjacent sheets closer together. The sheets can also be aligned so thatthe raised and/or depressed portions do not nest with each other, whichforms a gap between the adjacent sheets. The alignment can be used toform various open and closed channels for vapor adsorption between thesheets.

Sorbent Material Sheet Product

The sorbent material sheets described above are combined into a sorbentmaterial sheet product. The combination of the sorbent material sheetstakes advantage of one or more of the above described features, such asincreased surface area/volume ratio, reduced void space, improvedsorbent performance, etc. In general, the individual sorbent materialsheets are arranged next to each other to form a sorbent material sheetproduct that comprises sheets that are stacked, rolled, wound, folded,and/or laminated such that the surfaces of the sorbent material sheetsare in close proximity to, or adjacent to each other. Whatever thearrangement, the goal is to maximize the surface area of the sheetsexposed to the vapor, fluid, and/or gas stream and thus the performanceof the sorbent material sheets.

Stacked Sorbent Material Sheet Product: The stacked sorbent materialsheet product of the invention comprises two or more sorbent sheets eachdefining an upper surface and a lower surface, and having a knowncombined total surface area, wherein each sorbent sheet comprises asorbent material and a binder; where adjacent sorbent sheets are stackedand arranged such that adjacent upper and lower surfaces aresubstantially congruent with each other, and aligned to allow fluid flowat least between adjacent upper and lower surfaces.

This arrangement results in an improved BWC. For example, eachindividual sorbent material sheet may have a BWC of about 12, and thestacked sorbent sheet media has a BWC that is at least about 1-10%, atleast about 5-15%, at least about 2-20%, at least about 5-10%, or atleast about 7% higher than the sum of the BWC of the individual sheets.The sorbent sheet media of claim 1 wherein the stacked sorbent sheetproduct has a BWC at least about 5% higher than the BWC of an unstackedsheet having the same known surface area.

Performance improvements of the stacked sorbent material sheet productof the invention can also be measured as the performance of the producthaving a given amount of activated carbon versus the performance of thatsame amount and grade of activated carbon if provided within a canisterin a pelletized or powdered form. In some embodiments, the stackedsorbent sheet product has a BWC that is about 3% higher, about 5%higher, about 7% higher, about 9% higher, about 10% higher, about 12%higher, about 14% higher, and about 16% higher than the same amount andgrade of activated carbon within a canister in pelletized or powderedform. Ranges based on these amounts are also contemplated, such asperformance that is between about 5-14% higher, between about 5-10%higher, between about 10-16% higher, and so forth.

It should be noted that these improvements are only measured as betweenthe weights of the pelletized or powdered activated carbon and thestacked sorbent material sheet product, without accounting for otherimprovements of the stacked sorbent material sheet product. One keydifference, described above, is the omission of a rigid canister bodythat would otherwise be required. The omission of the rigid canisterbody, which is needed in prior art systems involving pelletized orpowdered activated carbon because the loose activated carbon cannotsupport itself, drives further weight savings and therefore even furtherperformance for a given weight.

The stacked sorbent sheet product has a BWC at least 10% higher than theBWC of a pelletized/powdered form of the same amount by weight of thesorbent material in the sorbent sheet. The stacked sorbent sheet producthas a butane working capacity greater than about 10 g/100 cc. Thestacked sorbent sheet product has a butane working capacity of about 7.0g/100 cc to about 30 g/100 cc, or greater than about 12 g/100 cc, orgreater than about 13 g/100 cc, or greater than about 14 g/100 cc, orgreater than about 15 g/100 cc, or greater than 20 g/100 cc. Ranges arealso contemplated, such as about 10-20 g/cc, about 10-12 g/cc, about10-14 g/cc, about 12-14 g/cc, about 12-15 g/cc, and about 15-20 g/cc.

In some embodiments, the stacked sheets are held in a spaced apartrelationship which controls one or more of void volume, flow rate,pressure drop, and other characteristics. Such spacing is achieved insome embodiments where at least one of the two or more sorbent materialsheets is corrugated. The spacing can also be achieved with variousfolds in the sheets, and can also be achieved by the correspondingraised and/or depressed portions of the sheets which are aligned to formgaps between the sheet. If the sheets are arranged deliberately so thatthe raised and/or depressed portions of the sheets do not nest betweensheets, this results in additional spacing between the sheets andpermits fluid flow in those portions. If the sheets are arrangeddeliberately so that at least some raised and/or depressed portions nestbetween sheets, this results in a tighter fitting stack of sheets anddecreases the spacing between the sheets, with a corresponding decreaseor even stop in fluid flow. Combinations of these features can be usedto form stacked sorbent sheet products with directed regions or channelsfor fluid flow and barriers or edge seals to prevent fluid leakage.These features for fluid flow can also include holes, cuts, or aperturesthrough one or more of the sheets in the stacked sorbent sheet product.

Each sorbent sheet defines opposed lateral edges which are substantiallyparallel to fluid flow. The congruent lateral edges of adjacent sorbentsheets may be separate from each other, bound together or somecombination thereof. In this manner, the edges of the stacked sorbentmaterial sheet product may be sealed, partially sealed, or unsealed. Thesealed or unsealed nature can be chosen to achieve desired results suchas modifying fluid flow rate and/or patterns or other properties.

In some embodiments, the stacked sorbent material product yields a voidvolume of about 10% or less. In some embodiments, the void volume isabout 8% or less, in some embodiments, the void volume is about 6% orless, in some embodiments, the void volume is about 4% or less.

In some embodiments, each sorbent sheet has a density of about 0.08 g/ccto about 1.5 g/cc.

In some instances, the sorbent material sheet product comprises at leasttwo populations of sorbent material particles, wherein each of the atleast two populations have different average particle diameters. See theabove description of the bimodal particle size distribution which wasdiscussed with respect to the individual sorbent material sheets. Thesame distribution ratios as between populations of sorbent particles arecontemplated with respect to product formed of multiple sorbent materialsheets. In some instances, the density of the sorbent material particlesachieved by the at least two populations is greater than the densityachieved by either population alone. The inclusion of a bimodal particlesize distribution can also be used to improve the mechanical propertiesof the sorbent material sheet product because it makes the polymericsheets much more resistant to shear forces.

In some instances, a sorbent material sheet product comprises at leasttwo sorbent material sheets, each of which has a defined upper surfaceand lower surface which have a combined total surface area, and whereineach sorbent material sheet comprises a sorbent material and a binder,and wherein each sorbent material sheet is stacked and arranged suchthat adjacent upper and lower surfaces of the separate sheets aresubstantially parallel and are aligned to allow fluid flow at leastbetween the adjacent upper and lower surfaces.

The sorbent material sheet product may have a BWC stacking multiplierratio of about 2.0, wherein the BWC stacking multiplier ratio is definedby the formula:

BWC stacking multiplier ratio=[(measured BWC of entire sorbent materialsheet product)/(measured BWC of individual sorbent material sheetoutside of product)]/number of sorbent material sheets in the sorbentmaterial sheet product.

The BWC stacking multiplier ratio may be at least about 1.0, at leastabout 1.1, at least about 1.2, at least about 1.3, at least about 1.4,at least about 1.5, at least about 1.6, at least about 1.7, at leastabout 1.8, at least about 1.9, at least about 2.0, at least about 2.1,at least about 2.2, at least about 2.3, at least about 2.4, at leastabout 2.5, at least about 2.6, at least about 2.7, at least about 2.8,at least about 2.9, and at least about 3.0. Additionally, endpoints canbe combined, for instance about 1.0-1.5, about 1.1-1.2, about 1.1-1.3,about 1.5-2.0, about 2.0-2.5, and about 2.5-3.0.

The sorbent material sheet product of claim 1, wherein the sorbentmaterial sheet product has a BWC value about 5%, about 10%, about 15%,about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, andabout 50% higher than the BWC of the same weight of sorbent material inpelletized or powdered forms. These can also be combined to formedranges, for example, between about 5-25% higher. The invention alsocontemplates that these amounts are the endpoints on ranges, such as atleast about 40% higher.

The sorbent material sheets in the sorbent material sheet product, maybe configured as being flat, wound in a spiral cylinder, wound in anelliptical form, wound in an elongate rectangular bar, folded, laminatedin an “S” shape, formed as concentric cylinders, formed as concentricellipses, formed as a concentric rectangular bar, or as combinations ofthese forms.

In some embodiments, the sorbent material sheet product will comprise asingle sorbent material sheet that is wound or rolled to achieve thedesired characteristics including, but not limited to density, voidspace, pressure drop, etc.

Wound/Rolled Sorbent Material Sheet Product: The sorbent material sheetproduct can also be wound or rolled as an alternative or in combinationwith stacked embodiments. A wound or rolled sorbent material sheetproduct comprises a sorbent sheet defining an upper surface and a lowersurface, and combined has a known total surface area, wherein thesorbent sheet comprises a sorbent material and a binder where thesorbent sheet is spiral wound to create adjacent sheet layers whichallow fluid flow around and between adjacent sheet layers.

Similar to the stacked sheet arrangement, the rolled sorbent sheetproduct has improved performance over the sorbent material sheets alone,and has improved performance over the equivalent weight of activatedcarbon that is provided in pelletized or powdered form.

The rolled arrangement results in an improved BWC for a given sheet areaversus the same area for individual sheets that are not rolled. Forexample, each individual sorbent material sheet may have a BWC of about12, and the rolled sorbent sheet media has a BWC that is at least about1-10%, at least about 5-15%, at least about 2-20%, at least about 5-10%,at least about 5%, or at least about 7% higher than the sum of the BWCof the individual sheets.

Performance improvements of the rolled sorbent material sheet product ofthe invention can also be measured as the performance of the producthaving a given amount of activated carbon versus the performance of thatsame amount and grade of activated carbon if provided within a canisterin a pelletized or powdered form. In some embodiments, the rolledsorbent sheet product has a BWC that is about 3% higher, about 5%higher, about 7% higher, about 9% higher, about 10% higher, about 12%higher, about 14% higher, and about 16% higher than the same amount andgrade of activated carbon within a canister in pelletized or powderedform. Ranges based on these amounts are also contemplated, such asperformance that is between about 5-14% higher, between about 5-10%higher, between about 10-16% higher, and so forth.

The rolled sorbent sheet product has a BWC at least 10% higher than theBWC of a pelletized/powdered form of the same amount by weight of thesorbent material in the sorbent sheet. The stacked sorbent sheet producthas a butane working capacity greater than about 10 g/100 cc. Thestacked sorbent sheet product has a butane working capacity of about 7.0g/100 cc to about 30 g/100 cc, or greater than about 12 g/100 cc, orgreater than about 13 g/100 cc, or greater than about 14 g/100 cc, orgreater than about 15 g/100 cc, or greater than 20 g/100 cc. Ranges arealso contemplated, such as about 10-20 g/cc, about 10-12 g/cc, about10-14 g/cc, about 12-14 g/cc, about 12-15 g/cc, and about 15-20 g/cc.

A rolled sorbent sheet product as described herein has a generallycylindrical shape having a length substantially greater than itsdiameter, although any dimension can be employed, including conical, orfrustro-conical variations, as well as ellipsoids, or other shapes.

The density of the rolled sorbent sheet product may be computed based onthe formulas below:

${{Roll}{Density}{Calculations}\left( {U.S.{units}} \right)}{{p\left( \frac{lb}{{ft}^{2}} \right)} = {(3) \star \frac{{BW} + L}{\left( {\frac{{OD}^{2}}{4} - \frac{{ID}^{2}}{4}} \right) \star \pi}}}{{BW}:{Basis}{Weight}\left( \frac{oz}{{yd}^{2}} \right)}{L:{Length}{on}{Roll}({yd})}{{OD}:{Outer}{Roll}{Diameter}({in})}{{ID}:{Inner}{Roll}{{Diameter}/{Core}}{Diameter}({in})}{W:{Machine}{width}{or}{roll}{length}({in})}{p:{Roll}{Density}\left( \frac{lb}{{ft}^{3}} \right)}{{Roll}{Density}{Calculations}\left( {{SI}{units}} \right)}{{p\left( \frac{kg}{m^{3}} \right)} = {(1000) \star \frac{{BW} + L}{\left( {\frac{{OD}^{2}}{4} - \frac{{ID}^{2}}{4}} \right) \star \pi}}}{{BW}:{Basis}{Weight}\left( \frac{g}{m^{2}} \right)}{L:{Length}{on}{Roll}(m)}{{OD}:{Outer}{Roll}{Diameter}({mm})}{{ID}:{Inner}{Roll}{{Diameter}/{Core}}{Diameter}({mm})}{W:{Machine}{width}{or}{roll}{length}({mm})}{p:{Roll}{Density}\left( \frac{kg}{m^{3}} \right)}$

The rolled sorbent sheet product may be wound to an average roll densityof about 80-1500 kg/m³, about 500-2000 kg/m³, about 750-1500 kg/m³,about 900-1200 kg/m³, about 900-1050 kg/m³, about 400-500 kg/m³, about500-600 kg/m³, about 500-550 kg/m³, about 600-650 kg/m³, about 650-700kg/m³, and about 700-750 kg/m³.

The rolled sorbent sheet product has a butane working capacity greaterthan about 10 g/100 cc. In some embodiments, the rolled sorbent sheetproduct has a butane working capacity of about 7.0 g/100 cc to about 30g/100 cc. The rolled sorbent sheet product may also have butane workingcapacities that are the same as the above described sorbent sheetproducts which are not rolled.

Similar to the discussion above with respect to the stacked sorbentmaterial sheets, the wound or rolled sorbent material sheets may includemultiple particle size distributions or populations of the adsorbentpelletized or powdered activated carbon. The same ratios arecontemplated as discussed above. Similar to the discussion above, thisresults in greater performance because it enables a larger amount of theactivated carbon to be incorporated into the sheets which are formedinto the rolled sorbent sheet product.

As used herein, wound or rolled sorbent sheet products refer to any formof layering of one or more sorbent material sheets by winding, spiralwinding, concentric layering of tubular (of any cross-sectional shape,e.g. round, elliptical, square, triangular, rectangle, etc.) orcombination thereof. For example, a single sorbent material sheet may bespiral wound along its length to form a cylindrical-shaped rolledsorbent material sheet product. As another example, a plurality ofsorbent material sheets can be stacked and then wound together to form asimilar cylindrical shape. As another alternative, several sheets eachformed into a cylinder having a slightly different diameter from thenext can be arranged such that they from concentric rings incross-section of a similarly sized cylinder. Various combinations ofthese and other arrangements may be used to fill the space within anyshape of housing or canister, as described elsewhere herein.

As noted above with respect to the sorbent material sheets, the binderis selected from polytetrafluoroethylenes (PTFE or TEFLON),polyvinylidene fluorides (PVF2 or PVDF), ethylene-propylene-diene (EPDM)rubbers, polyethylene oxides (PEO), UV curable acrylates, UV curablemethacrylates, heat curable divinyl ethers, polybutylene terephthalate,acetal or polyoxymethylene resin, fluoroelastomers, perfluoroelastomers(FFKM) and/or tetrafluoro ethylene/propylene rubbers (FEPM), aramidpolymers, para-aramid polymers, meta-aramid polymers, poly trimethyleneterephthalate, ethylene acrylic elastomers, polyimide, polyamide-imides,polyurethanes, low density and high density polyethylene, polypropylene,biaxially oriented polypropylene (BoPP), polyethylene terephthalate(PET), biaxially oriented polyethylene terephthalate (BoPET),polychloroprene, and copolymers and combinations thereof.

The Housing

The invention also contemplates the use of a housing which partially ortotally encapsulates the sorbent material sheets. The housing may beconfigured in a variety of shapes, for example tetrahedrons, cubes andcuboidal shapes, cylinders, spheres, hyperboloids of a single sheet,conical shapes, ellipsoidal shapes, rectangular shapes, hyperbolicparaboloid shapes, elongate bar shapes, paraboloids, and combinations ofthese shapes. The combinations may be selected to have differentsections each of which have different shapes or portions of differentshapes. The housing may also include sections which are separated andare connected by an additional part, for instance, at least one hose ortube which is designed to transfer fuel vapors as needed, or a thinportion of housing that contains the sorbent material sheets. Thehousing may also be configured with no shape, for example as a flexiblebag or pouch containing the sorbent material sheets.

One major advantage of the invention is that the use of the sorbentmaterial sheets are both flexible and self-supporting and can belaminated, rolled, wound, folded, or stacked in a variety ofconfigurations within the housing to suit different mechanicalrequirements within the tight confines of a vehicle. In suchembodiments, the housing would be designed to conform or fit the spacesthat are available for the device to be stored. For instance, thehousing can be sized and shaped to fit in spaces within or surroundingwheel wells, driveshafts, batteries for hybrid powertrains, spare tires,tire changing tools, tire patching tools, vehicle trunks or otherstorage spaces, vehicle bumpers and bodywork panels, exhaust systems,other emissions control equipment such as urea or other injection tanks,fuel lines, vehicle frames, suspension components, engine compartment,under passenger compartment seats, within passenger compartment seats,and other spaces which are too small or too difficult to reach to beeffectively utilized for passenger or cargo space.

To further reduce weight and size and take advantage of theself-supporting sorbent material sheets, the housing can be in the formof a thin walled bag or pouch. This is possible because the sorbentmaterial sheets have some mechanical structure and are self-supportingand so do not require a rigid outer container as in conventionalcanisters. The film materials that form the bag can have thicknesses ofabout 10 μm to about 250 μm. In other embodiments, the bag film can havethicknesses of about 20 μm to about 175 μm, and the bag film can havethicknesses of about 50 μm to about 125 μm.

The bag or pouch may be formed of any materials which are used in fuelsystems, and particularly are formed of materials which are designed towithstand the chemical effects of the fuel vapors contained. Bagmaterials include polytetrafluoroethylenes (PTFE or TEFLON),polyvinylidene fluorides (PVF₂ or PVDF), ethylene-propylene-diene (EPDM)rubbers, polyethylene oxides (PEO), UV curable acrylates, UV curablemethacrylates, heat curable divinyl ethers, polybutylene terephthalate,acetal or polyoxymethylene resin, fluoroelastomers such asperfluoroelastomers (FFKM) and tetrafluoro ethylene/propylene rubbers(FEPM), aramid polymers such as para-aramid and meta-aramid polymers,poly trimethylene terephthalate, ethylene acrylic elastomers, polyimide,polyamide-imides, polyurethanes, low density and high densitypolyethylene, polypropylene, biaxially oriented polypropylene (BoPP),polyethylene terephthalate (PET), biaxially oriented polyethyleneterephthalate (BoPET), polychloroprene, and copolymers and combinationsthereof. The bag is typically thermoplastic for flexibility, but canalso be a combination with amounts of thermoset or can be in the form ofa cured rubber or an elastomer.

The housing, bag, or pouch may also be designed to act as a vaporbarrier to the adsorbed fuel vapors contained therein. This barrierproperty may be inherent to the polymer itself, or may be achievedthrough the use of at least one barrier additive and/or at least onebarrier layer. Examples of barrier additives which can be formed as alayer or as a particulate filler include polymers such as epoxy,polyamide, polyamide imides, fluoropolymers, fluororubbers, andcombinations of those. Barrier layers can also be made of metals such asaluminum, steel, titanium, and alloys of those. The metal barrier layerscan be formed by conventional mechanical means, such as coextrusion oradhering with the other layers of the housing, or they can be chemicallydeposited, such as by chemical vapor deposition or electroplating. Themetal barrier layer can be formed from a foil having a thickness of lessthan about 25 μm, less than about 20 μm, less than about 15 μm, lessthan about 10 μm, or less than about 5 μm.

The housing and its materials may also be selected to be compatible with“ship in a bottle” fuel systems. In such systems, many or all of thefuel system components, including the fuel pumps, ORVR, fuel filters,valves, and other components are fitted within the vehicle fuel tank.Such systems are advantageous because they reduce assembly time and theamount of space required by the fuel system. In such systems, thehousing should have materials which are capable of being immersed in theselected fuel, typically gasoline, for extended periods of time withinthe vehicle fuel tank, while also being able to withstand the effects ofthe adsorbed fuel vapors within.

The housing may also be a thin metal housing. The thin metal housing canbe formed of flexible or rigid metals such as steel, aluminum, titanium,and alloys of those. The metal housing can be formed from a foil havinga thickness of about 5-100 μm, or about 10-250 μm. In some embodiments,the foil may be as thick as about 1 mm. Whether the housing is flexibleor rigid depends on the selection of the material, the thickness, andany treatments that have been applied to the metals, such as heattreatments or hot or cold working.

In some embodiments, the housing for the sorbent material sheets may beomitted entirely, with the sorbent material sheets being containedwithin the fuel tank itself. In such configurations, the sorbentmaterials sheets can be attached to a portion of the interior of thefuel tank that does not regularly come in contact with liquid fuel andwhich is free to adsorb fuel vapors. This portion is typically the topor sides of the fuel tank, or combinations of those. The fuel tank mayalso include a recessed portion on the top or the sides which isdesigned to include the sorbent material sheets and allow the sorbentmaterial sheets to adsorb fuel vapors. Such embodiments where sorbentmaterial sheets are attached to the interior portions of the fuel tanknot only offer maximum space savings and weight savings by omitting thecanister structure, but also simplify manufacturing and installationbecause the sheets are already installed within the fuel tank duringvehicle assembly.

The housing can also be eliminated by forming a rolled or folded sorbentsheet and then selectively curing the outer sheets so that they form adurable, cured shell that acts as a support for the rolled or foldedsorbent sheets within. Such selective curing can be accomplishedthermally or with a chemical bath, or via actinic radiation, such asultraviolet light or by electron beam curing.

In embodiments where the sorbent material sheets omit the housing andare contained within the vehicle fuel tank itself, the sorbent materialsheets may be attached to the fuel tank in a variety of ways. Thesorbent material sheets can be fastened using mechanical fasteners suchas screws, rivets, or clamps, or the sorbent material sheets may befastened using an adhesive backing positioned between the fuel tank walland the sorbent material sheets. The adhesive backing may be a singlelayer of adhesive or a double sided adhesive tape or sheet. The adhesiveused in the adhesive backing may include pressure sensitive adhesives,UV curing adhesives, thermally curing adhesives, hot melt adhesives, andreactive multi-part adhesives. Adhesive compositions include acrylic and(meth)acrylic, acrylate and (meth)acrylate, epoxies in one- and two-partformulations, and urethane.

The sorbent material sheets may be applied during manufacturing in avariety of ways. In some embodiments, the fuel tank may be formed andthe sorbent material sheets are applied in a separate step where theadhesive is applied followed by the application of the sorbent materialsheets. In other embodiments, the sorbent material sheets are placed,with or without an adhesive backing as appropriate, on the inside of amold and the fuel tank is injected or blow molded around the sorbentmaterial sheets. In other embodiments, the sorbent material sheets maybe coextruded with panels of material which make up the sides of thefuel tank, and the edges of those panels are adhered or welded togetherto seal the final tank with the sorbent material sheets on the inside.

When the sorbent material sheets are contained within the vehicle fueltank without the housing, the fuel tank may include additional valvesand ports to accommodate the adsorption and desorption of fuel vapors inthe fuel tank. For example, during engine operation, air may beintroduced into the fuel tank to desorb the fuel vapors which arecontained in the sorbent material sheets, as well as those which arepresent in the tank. These desorbed fuel vapors are then sent to theengine for combustion during optimal cycles as required by the ECU.

When the sorbent material sheets are provided without a housing and arecontained within a tank, such as a vehicle fuel tank, they may bepositioned so that they are not regularly immersed in the volatileliquids typically contained within the tank. This ensures that thesorbent material sheets do not become prematurely saturated, and alsoensures that sufficient surface area is exposed to the vapors within thefuel tank to effect the adsorption of the vapors. The featurecontemplates that the sorbent material sheets can be placed in parts ofthe tank that are unfilled, such as the ullage or headspace of the tank,or near baffles which prevent the sloshing of liquids on the sorbentmaterial sheets. The sorbent material sheets may also be places in adedicated portion of the tank, such as a small chamber or niche, wherethe liquids cannot enter.

The devices of various embodiments may include a housing and the sorbentmaterial sheets described above. The housing may be any shape and can beconfigured for purifying gasses or liquids. For example, in someembodiments, the housing may be any shape such as, for example,cuboidal, cubic, or cylindrical. The sorbent material sheets may besized to fit within the housing and substantially fill a space withinthe housing through which the gas or liquid is passed. In someembodiments, two or more sorbent material sheets may be stacked tosubstantially fill the housing, and in other embodiments, the sorbentmaterial sheets may be rolled to form a spiral wound sheet or pressed toform a stacked sheet. In some embodiments, the stacked or pressed sheetsmay be such that the sides of adjoining sheets are substantiallycontiguous. In other embodiments, stacked or pressed sheets may bepositioned such that adjoining sheets are spaced. For example, incertain embodiments, the sheets may be corrugated, having sorbentmaterial sheets that form a series or parallel ridges and furrows, andin some embodiments, corrugated sorbent material sheets may be separatedby flat sorbent material sheets. The corrugated sorbent material sheetsmay be disposed within the housing in a stacked or rolled/spiral woundform.

In various embodiments, the void fraction may be about 30% to about 32%less than the void volume for current devices, and in some embodiments,the void fraction may be less than 10%. For example, the devices mayhave a void fraction of about 45% to about 2%, about 35% to about 5%,about 25% to about 7%, or any individual void fraction or rangeencompassed by these example ranges. The devices of various embodimentsmay exhibit less flow restriction, e.g. pressure drop, than deviceshaving granular or pelleted sorbent materials. Thus, more adsorbentmaterial can be incorporated into such devices without reducing the flowrate of the device.

The devices of such embodiments may have butane working capacities(“BWC”) of greater than about 5.0 g/100 cc, and in some embodiments, thedevices may have a BWC of about 4.0 g/100 cc to about 20 g/100 cc, 5.0g/100 cc to about 18 g/100 cc, about 7.0 g/100 cc to about 16 g/100 cc,or about 8.0 g/100 cc to about 15 g/100 cc, or any individual BWC orrange encompassed by these example ranges. The devices may exhibit apressure drop that is at most equal to a conventional dense pack bed ofpowders, pellets, or granules of activated carbon or other activatedcompounds. This feature is advantageous because it ensures that theinventive sorbent material sheet product, whether stacked, rolled,wound, or otherwise configured, still has the same ability to processand transfer vapors and gases as conventional devices, despite theincreased sorbent performance.

When the sorbent material product, stacked or rolled, is combined with ahousing, it is useful as a vapor loss canister or other device. As notedabove, the shapes and properties achieved via the stacked or rolledproducts allow for unique placement and improved performance.

In accordance with some embodiments, a vapor loss canister comprises ahousing having at least one sidewall defining an internal space, asorbent sheet product, such that the sorbent sheet media is sized andconfigured to fit within the housing and fill substantially the entireinternal space within the housing, wherein the internal space issubstantially free of additional internal material other than thesorbent sheet media. That is, traditional vapor loss canisters requiresprings, filters, support substrates, etc. to hold and maintain theloose carbon powder or pellets. Because the sorbent sheets aresubstantially self-supporting, these additional support structure arenot needed. This allows for the inclusion of more material or the use ofa smaller canister without sacrificing performance.

In some embodiments, the sorbent sheet product comprises a stackedsorbent sheet media comprising as described above. In such instances,the housing or canister can take any shape as discussed above, but insome embodiments, is relatively flat and flexible for housing stackedsorbent sheet media that has a height substantially less than its lengthor width. In these instances, the housing may be a flexible bag orpouch, as discussed above.

In some instances the canister is adapted for placement atop or evenwithin a fuel tank.

In some embodiments, sorbent sheet material product comprises a rolledsorbent sheet product as described above. In some instances, at least aportion of the housing sidewall defines a filter substantially withoutoccupying any internal canister space.

In some embodiments, a fuel tank may be provided with integral vaporadsorption. Such tanks comprise a tank structure, and at least onesorbent sheet material product, either stacked or rolled, at least onefastening device which fastens the sorbent material product to a surfaceof the tank that is not regularly immersed in the volatile liquidscontained within the tank. The fastening device may be an adhesive layerwhich is formed between one surface of the sorbent material product anda wall of the tank.

Such adhesive may be at least one of pressure sensitive adhesives, UVcuring adhesives, thermally curing adhesives, hot melt adhesives,reactive multi-part adhesives, acrylic and (meth)acrylic adhesives,acrylate and (meth)acrylate adhesives, epoxies adhesives in one- andtwo-part formulations, urethane adhesives, and copolymers andcombinations thereof.

The tank may further include one or more of at least one fuel pump(s),fuel sending line(s), fuel return line(s), atmospheric vent line,port(s), valve(s), sensor(s), air inlet(s), open cell foam, baffle(s),bladder(s) and combinations of those.

In some embodiments, the tank is a fuel tank with a “ship in a bottle”configuration.

Some embodiments provide an onboard refueling vapor recovery apparatuscomprising the sorbent material sheet product as described herein. Theonboard refueling vapor recovery apparatus may include a vapor adsorbingcanister as described herein. The onboard refueling vapor recoveryapparatus may include a tank with integral vapor adsorption of claim 22.

Additional Components

The invention may include sensors such as a fuel composition sensor. Thefuel composition sensor may be used to detect the mixture of gasolineand ethanol contained within the housing and the sorbent material, andthis information may be communicated to the ECU so that vapors which arelater released to the engine can be more precisely used during enginecombustion. Other sensors include temperature sensors, vapor pressuresensors, oxygen sensors, and the like. The sensors can operate onprinciples of electrochemical interaction, electronic such asthermocouples, electromechanical, refractive index, infraredspectroscopy, and others depending on the type of information that isrequired for the ECU. The sensors can be included alone or incombination within the housing, or, if no housing is specified, withinthe area that contains the sorbent materials sheets. The sensors can beincluded in holes or notches which are cut from the sheet, or in spacesbetween the sheets with the sheets wrapped or folded around the sensors.

The invention may include inlets, outlets, hoses, and associated valvesto control the flow of fuel vapor to and from the sorbent materials ofthe invention. The openings may static or they may have valves that areopened and closed as required by the ECU to control the flow of vaporinto and out of the sorbent sheets of the invention. For example, duringrefueling, outlet valves remain closed to ensure that displaced fuelvapors do not escape into the atmosphere. However, when the engineoperates and the ECU requests it, at least one outlet valve may open toallow the release of adsorbed vapor into the engine to allow itscombustion. There may also be included a vent and valve to theatmosphere in case there is too much fuel vapor for the sorbent materialsheets of the invention to safely adsorb. There may further be includedan inlet and valve for air or other gases, such as inert exhaust gases,which is used to desorb the fuel vapor as it is being sent to the enginefor combustion.

The invention also contemplates the inclusion of and integration withother components which make up ORVR systems and devices. These othercomponents may include active compressors and condensers, fuel tankheaters, fuel tank heat exchanging coils for cooling enclosed fuels,fuel filler necks, fuel filler ports, including capless fuel fillerports, vents for fuel vapors, fuel lines for sending fuel, fuel returnlines, vents and vehicle rollover valves, fuel pumps, and air intake orpurge valves.

The invention further contemplates devices and structures which may becombined with the sorbent material sheets to improve or control theadsorption and desorption of fluids and gases. For example, fans orpumps may be included to force the fluids or vapors over the sorbentmaterial sheets as they are assembled, allowing the sorbent materialsheets to be packed or wound tighter or allowing larger devices thanwould otherwise be possible with the same amount of fluid diffusion overthe sheets. Alternatively, the devices can include resistance elementheaters, or Peltier effect heaters or coolers which are designed to heatand/or cool the fluids and thus force their movement over the sorbentmaterial sheets of the claimed invention. For instance, heated,expanding fluid may vent upwards and draw in more fluid at the bottom ofa rolled or wound article that is oriented vertically to take advantageof the effects of gravity.

Other Uses

In addition to automotive uses, the inventors contemplate that thesorbent sheets of the claimed invention can be used in any instancewhere a tank or other enclosed space is designed to contain volatileliquids, in particular volatile hydrocarbons such as fuels, solvents,and other volatile compounds. Examples include but are not limited tofuel tanks in aircraft, fuel tanks in ships and other marine vehicles,fuel tanks in trucks, chemical tanks in railroad cars, barges, ships,trucks, vehicles, and other bulk carriers, and stationary chemicaltanks. The sorbent material sheets of the claimed invention can also beattached or adhered to the walls of confined spaces where the presenceof volatile compounds would be detrimental, for example, in chemicalfacilities where operators and maintenance staff must periodicallyaccess the space. Such sorbent material sheets, when used in suchcombined spaces, can not only increase safety for operators andmaintenance staff, but they can also reduce the need for cumbersomeprotective gear.

In some embodiments, the devices may not filter microscopic particles,and therefore will have utility outside the fuel vapor recovery arena.Devices containing granular or pelleted sorbent materials filterparticles that are larger than about 1% of their diameter therebyremoving these particles from gases or liquids that are treated usingthe device. Because devices containing stacked or rolled/spiral woundsorbent material sheets allow such particles to pass through withoutfiltering, the devices of various embodiments may be useful forfiltering biological fluids such as blood, where red and white bloodcells and platelets and the like must pass through the filter withoutbeing physically filtered out of the blood. Other contaminates may beadsorbed onto the sorbent material sheets and removed from the bloodfiltrate

EXAMPLES

Although the present invention has been described in considerable detailwith reference to certain preferred embodiments thereof, other versionsare possible. Therefore the spirit and scope of the appended claimsshould not be limited to the description and the preferred versionscontained within this specification. Various aspects of the presentinvention will be illustrated with reference to the followingnon-limiting examples.

As was discussed above, BWC is a measure of the performance of activatedcarbon. BWC is determined for a sample by measuring the ability of theactivated carbon to adsorb and desorb butane from dry air underspecified conditions, and measures the difference between the butaneadsorbed at saturated and the butane retained per unit volume of carbonafter a specified purge. BWC can be tested in several ways, includingprocedures specified by ASTM International and which are known to thoseof skill in the art. Specifically, testing can follow ASTM D5228, whichincludes revisions D5228-16, D5228-92(2015), D5228-92(2005), andD5228-92(2000).

In Examples 1-4, the carbon sheets were spiral wound to yield 10% voidfraction, which give about a 30% performance improvement over theactivated carbon (“PAC”) alone. The void fraction of comparativegranular or powdered beds of activated carbon, similar to ComparativeExample 1, was approximately 40% void fraction by volume. The Examplesand Comparative Example are described below.

Example 1

Activated carbon films were made from CPL (CT #14299-8), which is anactivated carbon that is wood based and which is activated usingphosphoric acid. Films were also made from CPW (CT #14299-10), which isan activated carbon that is wood based and which is activated usingphosphoric acid. The activated carbons were pulverized in a mechanicalmortar and pestle and mixed with 9% PTFE powder. The resultingcomposition had a bread dough-like consistency. The composition wasrolled to form sheets having thicknesses of 0.448 mm (CT #14299-8 1),0.411 mm (CT #14299-8 2), 0.459 mm (CT #14299-10 1), and 0.439 mm (CT#14299-10 2).

Example 2

Activated carbon sheets were prepared as described in Example 1 usingBVC-11 8×25 activated carbon, which is a nutshell based activated carbonthat is activated with phosphoric acid. This formed sample CT #14266-1.A sample was also formed with BVC-11 8×35, which is also a nutshellbased activated carbon that is activated with phosphoric acid. Thisformed sample CT #14266-2. The formed sheets had a thickness of 0.330 mm(CT #14266-1 1), 0.334 mm (CT #14266-1 2), 0.327 mm (CT #14266-1 3),0.317 mm (CT #14266-2 1), 0.307 mm (CT #14266-2 2), and 0.328 mm (CT#14266-2 3).

Butane Working Test—Examples 1 and 2

Activated carbon sheets prepared in Examples 1 and 2 were tested forbutane adsorption using the butane working test. In this test, thesheets were rolled and placed in tubes. Butane was added to the tubesand butane adsorption was measured. The Tactic experiments, used topredict the BWC performance, were run on small stacks of 5 slat sheets.Results are illustrated in TABLES 1 and 2:

TABLE 1 (Example 2) 14266-1 14266-2 Tube vol. (cc) 3.8465 3.8465 Sheetwt. (g) 6.3604 6.0009 Sheet thick. (cm) 0.033 0.0315 Sheet vol. (cc)11.22 10.71 Sheet dens. (g/cc) 0.566881 0.566881 BWC sheet 16.1 14.14measured (g/100 cc) BWC sheet tactic 16.48 15.59 predicted (g/100 cc)BWC PAC 12.10 12.20 measured (g/100 cc) BWC PAC tactic 11.98 12.31(g/100 cc)

TABLE 2 (Example 1) CT-14299-8 CT-14299-10 Tube vol. (cc) 16.504 16.504Sheet wt. (g) 4.10 3.16 Sheet thick. (cm) 0.411 0.439 Sheet vol. (cc)9.92 7.90 Sheet dens. (g/cc) 0.413 0.404 BWC sheet 12.32 12.41 measured(g/100 cc) BWC sheet tactic 12.22 12.93 predicted (g/100 cc) BWC PAC 7.99.6 measured (g/100 cc) BWC PAC tactic 9.59 8.89 (g/100 cc)

Example 3

Activated carbon sheets were prepared as in Examples 1 and 2, but usinggranular activated carbon #3445-32-4. The activated carbon sheets werealso not rolled as tightly as in prior Examples 1 and 2, which Theresultant sheets were tested for butane adsorption using the butaneworking capacity test. In these two tests, two separate stacks of 20sheets of 0.45 mm thickness were cut in rectangles of 2.2 cm×7.5 cm±10%,sealed at the side edge with double sided tape of 0.05 mm thickness and2 mm width. In this configuration, tape thickness defined the averagesheet spacing. Total height of each of the stacks of 20 sheets with tapespacers was 1 cm. These stacks of sheets were then placed in large 2.54cm diameter cylindrical glass tubes for butane adsorption/desorptiontesting. The excess volume between the rectangular stack of sheets andthe walls of the cylindrical glass tube were filled with closed cellexpanded foam to take up the excess volume and sealed to avoid bypassgas flow past the inserted test samples. The butane or air was forced toflow in the 0.05 mm gaps between the 20 sheets. The flow rate and volumeof the stacks of sheets was selected to maintain ASTM working capacityprocedure. The ASTM procedure was followed with the exception of the useof the stack of sheets rather than a granule bed, the use of the closedcell expanded foam for sealing, and the required larger cylindricalglass tube arrangement to accommodate the rectangular stack of sheets.

During the modified ASTM procedure, butane or air was forced to flow inthe 0.05 mm gaps between the 20 sheets, with the flow rate and volume ofthe stacks of sheets kept to ASTM specifications for working capacity.The results of Example 3 are in Table 3 below.

Comparative Example 1

A comparative example was also prepared using the same granularactivated carbon #3445-32-4 as in Example 4, but without forming thegranular activated carbon as part of a sheet or roll. The granulatedactivated carbon was tested per ASTM procedure. The results of this testare in Table 3 below.

TABLE 3 (Example 3 and Comparative Example 1) Granular activated carbonStacked 0.45 mm sheets (Comparative Example 1) (Example 3) #3445-32-4#3445-32-4-stack 1 #3445-32-4-stack 2 Tube vol. minus 16.7 16.4 15.5foam volume if present(cc) Carbon wt. (g) 6.513 7.885 7.465 Sheetthickness — .045 0.045 (cm) Granular bed or 16.7 16.4 15.5 Stacked sheetvol. (cc) Granular bed or 0.389 .534 .534 individual Sheet density(g/cc) BWC (g/100 cc) 9.33 10.25 10.83 BWC % — 9.9% 16.0% improvement

Conclusion and Summary of Examples 1-3 and Comparative Example 1

A summary of relevant data appears in Table 4 below:

TABLE 4 Summary of Data Sheet Thickness Density BWC Example TestDescription (cm) (g/cm³) (g/100 cm³) Ex. 1 CT#14299-8 Wood based 0.4110.413 12.32 activated carbon CPL Ex. 1 CT#14299-10 Wood based 0.4390.404 12.41 activated carbon CPW Ex. 2 CT#14266-1 BVC-11 0.033 0.56688116.1 (nutshell) activated carbon 8 × 25 Ex. 2 CT#14266-2 BVC-11 0.03150.566881 14.14 (nutshell) activated carbon 8 × 35 Ex. 3 #3445-32-4- GAC,20 0.045 0.534 10.25 stack 1 sheet stack Ex. 3 #3445-32-4 GAC, 20 0.0450.534 10.83 stack 2 sheet stack Comp. Ex. 1 #3445-32-4 Granular N/A0.389 9.33 Activated Carbon (GAC)

The invention claimed is:
 1. A vapor adsorbing canister, comprising asorbent material sheet product that includes: at least two sorbentmaterial sheets, each of which has a defined upper surface and lowersurface which have a combined total surface area, wherein each sorbentmaterial sheet comprises a sorbent material and a binder, the bindercomprising at least one of polytetrafluoroethylenes (PTFE or TEFLON),polyvinylidene fluorides (PVF2 or PVDF), ethylene-propylene-diene (EPDM)rubbers, polyethylene oxides (PEO), UV curable acrylates, UV curablemethacrylates, heat curable divinyl ethers, polybutylene terephthalate,acetal or polyoxymethylene resin, fluoroelastomers, perfluoroelastomers(FFKM) and/or tetrafluoro ethylene/propylene rubbers (FEPM), aramidpolymers, para-aramid polymers, meta-aramid polymers, poly trimethyleneterephthalate, ethylene acrylic elastomers, polyimide, polyamide-imides,polyurethanes, low density and high density polyethylene, polypropylene,biaxially oriented polypropylene (BoPP), polyethylene terephthalate(PET), biaxially oriented polyethylene terephthalate (BoPET),polychloroprene, and copolymers and combinations thereof, wherein eachsorbent material sheet is stacked and arranged such that adjacent upperand lower surfaces of the separate sheets are substantially parallel andare aligned to allow fluid flow at least between the adjacent upper andlower surfaces, wherein the sorbent material sheet product has a voidvolume of about 2% to about 25%, and a housing at least partiallyencapsulating the sorbent material sheet product.
 2. The vapor adsorbingcanister of claim 1, wherein the sorbent material sheet product has aBWC stacking multiplier ratio of about 1.1 to about 1.3, wherein the BWCstacking multiplier ratio is defined by the formula:BWC stacking multiplier ratio=[(measured BWC of entire sorbent materialsheet product)/(measured BWC of individual sorbent material sheetoutside of product)]/number of sorbent material sheets in the sorbentmaterial sheet product.
 3. The vapor adsorbing canister of claim 1,wherein the individual sorbent material sheets, measured individually,have BWC values that are 5-15% higher than the BWC of the same weight ofsorbent material in pelletized or powdered forms.
 4. The vapor adsorbingcanister of claim 1, wherein at least one of the sorbent material sheetsare configured as being flat, wound in a spiral cylinder, wound in anelliptical form, wound in an elongate rectangular bar, folded, laminatedin an “S” shape, formed as concentric cylinders, formed as concentricellipses, formed as a concentric rectangular bar, or as combinations ofthese forms.
 5. The vapor adsorbing canister of claim 1, wherein atleast one of the sorbent material sheets has raised and/or depressedportions.
 6. The vapor adsorbing canister of claim 5, wherein the raisedand/or depressed portions are present on adjacent sheets and are nested.7. The vapor adsorbing canister of claim 5, wherein the raised and/ordepressed portions are present on adjacent sheets and are not nested. 8.The vapor adsorbing canister of claim 1, wherein each individual sorbentmaterial sheet has a density of about 0.08 g/cc to about 1.5 g/cc. 9.The vapor adsorbing canister of claim 1, wherein the sorbent materialsheet product has a BWC greater than about 10 g/100 cc.
 10. The vaporadsorbing canister of claim 1, wherein the sorbent material sheetproduct has a BWC of about 7.0 g/100 cc to about 30 g/100 cc.
 11. Thevapor adsorbing canister of claim 1, wherein the sorbent material sheetscomprise sorbent material particles having at least two populationshaving different average particle diameters, and wherein the averageparticle diameters of the two populations have ratios of about 1:2 toabout 1:10.
 12. The vapor adsorbing canister of claim 1, wherein theamount of binder and the amount of sorbent material sheet products arepresent in a gradient such that the amount of binder is highest at anouter portion of the sorbent material sheet product, and that the amountof binder is lowest at an inner portion of the sorbent material sheetproduct.
 13. The vapor adsorbing canister of claim 1, wherein at leastone sorbent material sheet includes holes, cuts, or apertures.
 14. Thevapor adsorbing canister of claim 1, wherein the binder housingcomprises polytetrafluoroethylenes (PTFE or TEFLON), polyvinylidenefluorides (PVF2 or PVDF), ethylene-propylene-diene (EPDM) rubbers,polyethylene oxides (PEO), UV curable acrylates, UV curablemethacrylates, heat curable divinyl ethers, polybutylene terephthalate,acetal or polyoxymethylene resin, fluoroelastomers, perfluoroelastomers(FFKM) and/or tetrafluoro ethylene/propylene rubbers (FEPM), aramidpolymers, para-aramid polymers, meta-aramid polymers, poly trimethyleneterephthalate, ethylene acrylic elastomers, polyimide, polyamide-imides,polyurethanes, low density and high density polyethylene, polypropylene,biaxially oriented polypropylene (BoPP), polyethylene terephthalate(PET), biaxially oriented polyethylene terephthalate (BoPET),polychloroprene, and copolymers and combinations thereof.
 15. A vaporadsorbing canister comprising: a rolled sorbent material sheet product,that includes: a sorbent material sheet defining an upper surface and alower surface and having a total surface area, and which comprises asorbent material and a binder, the binder comprising at least one ofpolytetrafluoroethylenes (PTFE or TEFLON), polyvinylidene fluorides(PVF2 or PVDF), ethylene-propylene-diene (EPDM) rubbers, polyethyleneoxides (PEO), UV curable acrylates, UV curable methacrylates, heatcurable divinyl ethers, polybutylene terephthalate, acetal orpolyoxymethylene resin, fluoroelastomers, perfluoroelastomers (FFKM)and/or tetrafluoro ethylene/propylene rubbers (FEPM), aramid polymers,para-aramid polymers, meta-aramid polymers, poly trimethyleneterephthalate, ethylene acrylic elastomers, polyimide, polyamide-imides,polyurethanes, low density and high density polyethylene, polypropylene,biaxially oriented polypropylene (BoPP), polyethylene terephthalate(PET), biaxially oriented polyethylene terephthalate (BoPET),polychloroprene, and copolymers and combinations thereof, wherein thesorbent material sheet is spiral wound to form adjacent sheet layerswhich allow fluid flow around and between adjacent sheet layers, whereinthe sorbent material sheet product has a void volume of about 2% toabout 25%, and a housing at least partially encapsulating the rolledsorbent material sheet product.
 16. The vapor adsorbing canister ofclaim 15, wherein the sorbent material sheet in its rolled form has aBWC that is at least 10% higher than the BWC of the same sorbentmaterial sheet in an unrolled form.
 17. The vapor adsorbing canister ofclaim 15, wherein the rolled sorbent material sheet product has a BWCthat is at least 10% higher than the BWC of a pelletized or powderedform of substantially the same amount of sorbent material in the sorbentsheet.
 18. The vapor adsorbing canister of claim 15, wherein the rolledsorbent material sheet product has a generally cylindrical shape havinga length that is greater than its diameter.
 19. The vapor adsorbingcanister of claim 15, wherein the rolled sorbent material sheet productis wound to an average roll density of 500-700 kg/m³.
 20. The vaporadsorbing canister of claim 15, wherein the rolled sorbent materialsheet product has a butane working capacity greater than about 10 g/100cc.
 21. The vapor adsorbing canister of claim 15, wherein the rolledsorbent material sheet product has a butane working capacity of about7.0 g/100 cc to about 30 g/100 cc.
 22. The vapor adsorbing canister ofclaim 15, wherein the rolled sorbent material sheet comprises at leasttwo populations of sorbent material particles, wherein each of the atleast two populations have different average particle diameters.
 23. Thevapor adsorbing canister of claim 15, wherein the rolled sorbentmaterial sheets comprise sorbent material particles having at least twopopulations having different average particle diameters, and wherein theaverage particle diameters of the two populations have ratios of about1:2 to about 1:10.
 24. The vapor adsorbing canister of claim 15, whereinthe housing is flexible.
 25. The vapor adsorbing canister of claim 15,wherein the housing comprises one or more of polytetrafluoroethylenes(PTFE or TEFLON), polyvinylidene fluorides (PVF₂ or PVDF),ethylene-propylene-diene (EPDM) rubbers, polyethylene oxides (PEO), UVcurable acrylates, UV curable methacrylates, heat curable divinylethers, polybutylene terephthalate, acetal or polyoxymethylene resin,fluoroelastomers perfluoroelastomers (FFKM) and/or tetrafluoroethylene/propylene rubbers (FEPM), aramid polymers, para-aramid,meta-aramid polymers, poly trimethylene terephthalate, ethylene acrylicelastomers, polyimide, polyamide-imides, polyurethanes, low density andhigh density polyethylene, polypropylene, biaxially orientedpolypropylene (BoPP), polyethylene terephthalate (PET), biaxiallyoriented polyethylene terephthalate (BoPET), polychloroprene, andcopolymers and combinations thereof.
 26. The vapor adsorbing canister ofclaim 15, wherein the shape of the housing substantially conforms to theshape of the enclosed rolled sorbent material sheet product.
 27. Thevapor adsorbing canister of claim 15, further comprising at least onestructure selected from tubes, inlet ports, outlet ports, sensors,valves, and fluid channels.
 28. An onboard refueling vapor recoveryapparatus comprising the vapor adsorbing canister of claim
 1. 29. Anonboard refueling vapor recovery apparatus comprising the vaporadsorbing canister of claim 15.